1. Field of Invention
The invention relates to a novel process for the preparation of 1,2,4-triazoline-3(2H)-ones, hereinafter also referred to in simplified form as triazolinones, a class of compound of general formula (I), ##STR4## where
X=O or S,
R.sup.1 =(C.sub.2 -C.sub.8) alkoxyalkyl, (C.sub.2 -C.sub.8) haloalkoxyalkyl, (C.sub.1 -C.sub.8) alkyl, (C.sub.1 -C.sub.8) haloalkyl, (C.sub.1 -C.sub.8) cyanoalkyl, (C.sub.2 -C.sub.8) alkylthioalkyl, (C.sub.2 -C.sub.8) alkylsulfinylalkyl, (C.sub.2 -C.sub.8) alkylsulfonylalkyl, (C.sub.7 -C.sub.8) arylalkyl for example benzyl, (C.sub.2 -C.sub.8) alkenyl, (C.sub.2 -C.sub.8) haloalkenyl, (C.sub.2 -C.sub.8) alkinyl, (C.sub.2 -C.sub.8) haloalkinyl, aryl for example naphthyl or phenyl, that may be substituted once or many times with halogen, (C.sub.1 -C.sub.3) alkyl or (C.sub.1 -C.sub.3) alkoxy, heteroaryl for example pyridine, where heteroaryl may optionally be substituted by halogen,
R.sup.2 and R.sup.3, independently of one another represent, H, (C.sub.2 -C.sub.6) alkoxyalkyl, (C.sub.2 -C.sub.6) haloalkoxyalkyl, (C.sub.1 -C.sub.6) alkyl, (C.sub.1 -C.sub.6) haloalkyl, (C.sub.1 -C.sub.6) cyanoalkyl, (C.sub.1 -C.sub.6) alkylthio, (C.sub.2 -C.sub.6) alkylthioalkyl, (C.sub.2 -C.sub.6) alkylsulfinylalkyl, (C.sub.2 -C.sub.6) alkylsulfonylalkyl, (C.sub.7 -C.sub.8) arylalkyl for example benzyl, (C.sub.2 -C.sub.6) alkenyl, (C.sub.2 -C.sub.6) haloalkenyl, (C.sub.2 -C.sub.6) alkinyl, (C.sub.2 -C.sub.6) haloalkinyl; aryl for example naphthyl or phenyl, that may be substituted once or many times with halogen, (C.sub.1 -C.sub.3) alkyl or (C.sub.1 -C.sub.3) alkoxy, heteroaryl for example pyridine, where
R.sup.1 and R.sup.2 may also be associated to form a ring to produce structure (II), ##STR5## where
n and m independently of one another are 0, 1, 2 or 3,
Z=CR.sup.4 R.sup.5, O, S, S(O), S(O).sub.2, N((C.sub.1 -C.sub.4)alkyl), N((C.sub.1 -C.sub.4)haloalkyl), C.dbd.O, C.dbd.N--R.sup.4 or C.dbd.S,
R.sup.4 =H, (C.sub.1 -C.sub.3) alkyl, halogen, (C.sub.1 -C.sub.6) alkoxy, (C.sub.1 -C.sub.6) haloalkyl, (C.sub.1 -C.sub.6) haloalkoxy, (C.sub.2 -C.sub.6) alkylcarbonyloxy or (C.sub.2 -C.sub.6) haloalkylcarbonyloxy,
R.sup.5 =H, (C.sub.1 -C.sub.3) alkyl or halogen, where R.sup.4 and R.sup.5, independently of one another, can substitute the ring once or many times and occupy up to 12 (m=3, n=3) positions,
Q stands for one of the radicals ##STR6## where
W=O or S,
R.sup.6 =H, halogen,
R.sup.7 =H, (C.sub.1 -C.sub.8) alkyl, (C.sub.1 -C.sub.8) haloalkyl, halogen, OH, OR.sup.12, SH, S(O).sub.p R.sup.12, COR.sup.12, CO.sub.2 R.sup.12, C(O)SR.sup.12, C(O)NR.sup.14 R.sup.15, CHO, CR.sup.14 =NOR.sup.21, CHCR.sup.22 CO.sub.2 R.sup.12, CH.sub.2 CHR.sup.22 CO.sub.2 R.sup.12, CO.sub.2 N.dbd.CR.sup.16 R.sup.17, NO.sub.2, CN, NHSO.sub.2 R.sup.18, NHSO.sub.2 NHR.sup.18, NR.sup.12 R.sup.23, NH.sub.2 or phenyl, optionally substituted by R.sup.24,
p=0,1 or 2, R.sup.8 =(C.sub.1 -C.sub.2) alkyl, (C.sub.1 -C.sub.2) haloalkyl, OCH.sub.3, SCH.sub.3, OCHF.sub.2, halogen, CN or NO.sub.2,
R.sup.9 =H, (Cl-C.sub.3) alkyl or halogen,
R.sup.10 =H, (C.sub.1 -C.sub.3) alkyl, halogen, (C.sub.1 -C.sub.3) haloalkyl, cyclopropyl, Vinyl, C.sub.2 -C.sub.8 -alkinyl, CN, C(O)R.sup.23,CO.sub.2 R.sup.23, C(O)NR.sup.23 R.sup.25, CR.sup.19 R.sup.20 CN, CR.sup.19 R.sup.20 C(O)R.sup.23, CR.sup.19 R.sup.20 CO.sub.2 R.sup.23, CR.sup.19 R.sup.20 C(O)NR.sup.23 R.sup.25, CHR.sup.19 OH, CHR.sup.19 OC(O)R.sup.23 or OCHR.sup.19 OC(O)NR.sup.23 R.sup.25, or, when Q equals Q-2, R.sup.9 and R.sup.10 can together with the carbon atom to which they are bound be C.dbd.O,
R.sup.11 =H, (C.sub.1 -C.sub.6) alkyl, (C.sub.1 -C.sub.6) haloalkyl, (C.sub.3 -C.sub.6) haloalkenyl, (C.sub.2 -C.sub.6) alkoxyalkyl, (C.sub.3 -C.sub.6) alkenyl, (C.sub.3 -C.sub.6) alkinyl, (C.sub.3 -C.sub.6) haloalkinyl, (C.sub.4 -C.sub.7) cycloalkylalkyl, ##STR7##
R.sup.12 =(C.sub.1 -C.sub.8) alkyl, (C.sub.3 -C.sub.8) cycloalkyl, (C.sub.3 -C.sub.8) alkenyl, (C.sub.3 -C.sub.8) alkinyl, (C.sub.1 -C.sub.8) haloalkyl, (C.sub.2 -C.sub.8) alkoxyalkyl, (C.sub.2 -C.sub.8) alkylthioalkyl, (C.sub.2 -C.sub.8) alkylsulfinylalkyl, (C.sub.2 -C.sub.8) alkylsulfonylalkyl, (C.sub.4 -C.sub.8) alkoxyalkoxyalkyl, (C.sub.4 -C.sub.8) cycloalkylalkyl, (C.sub.6 -C.sub.8) cycloalkoxyalkyl, (C.sub.4 -C.sub.8) alkenyloxyalkyl, (C.sub.4 -C.sub.8) alkinyloxyalkyl, (C.sub.3 -C.sub.8) haloalkoxyalkyl, (C.sub.4 -C.sub.8) haloalkenyloxyalkyl, (C.sub.4 -C.sub.8) haloalkinyloxyalkyl, (C.sub.6 -C.sub.8) cycloalkylthioalkyl, (C.sub.4 -C.sub.8) alkenylthioalkyl, (C.sub.4 -C.sub.8) alkinylthioalkyl, (C.sub.1 -C.sub.4) alkyl, substituted by phenoxy or benzyloxy, each ring optionally substituted by halogen, (C.sub.1 -C.sub.3) alkyl or (C.sub.1 -C.sub.3) haloalkyl, (C.sub.4 -C.sub.8) trialkylsilylalkyl, (C.sub.3 -C.sub.8) cyanoalkyl, (C.sub.3 -C.sub.8) halocycloalkyl, (C.sub.3 -C.sub.8) haloalkenyl, (C.sub.5 -C.sub.8) alkoxyalkenyl, (C.sub.5 -C.sub.8) haloalkoxyalkenyl, (C.sub.5 -C.sub.8) alkylthioalkenyl, (C.sub.3 -C.sub.8) haloalkinyl, (C.sub.5 -C.sub.8) alkoxyalkinyl, (C.sub.5 -C.sub.8) haloalkoxyalkinyl, (C.sub.5 -C.sub.8) alkylthioalkinyl, (C.sub.2 -C.sub.8) alkylcarbonyl, benzyl, optionally substituted by halogen, (C.sub.1 -C.sub.3) alkyl or (C.sub.1 -C.sub.3) haloalkyl, CHR.sup.19 COR.sup.13, CHR.sup.19 P(O)(OR.sup.13) CHR.sup.19 P(S) (OR.sup.13).sub.2, P(O) (OR.sup.13).sub.2, P(S)(OR.sup.13).sub.2, CHR.sup.19 C(O)NR.sup.14 R.sup.15, CHR.sup.19 C(O)NH.sub.2, CHR.sup.19 CO.sub.2 R.sup.13, CO.sub.2 R.sup.13, SO.sub.2 R.sup.13, phenyl, optionally substituted by R.sup.24, ##STR8##
R.sup.13 =(C.sub.1 -C.sub.6) alkyl, (C.sub.1 -C.sub.6) haloalkyl, (C.sub.3 -C.sub.6) alkenyl or (C.sub.3 -C.sub.6) alkinyl,
R.sup.14 and R.sup.16 =independently of one another, H or (C.sub.1 -C.sub.4) alkyl,
R.sup.15 and R.sup.17 =independently of one another, (C.sub.1 -C.sub.4) alkyl or phenyl, optionally substituted by halogen, (C.sub.1 -C.sub.3) alkyl or (C.sub.1 -C.sub.3) haloalkyl, or
R.sup.14 and R.sup.15 can, together with the nitrogen atom that binds them, form a piperidinyl-, pyrrolidinyl- or morpholinyl-ring, each ring optionally substituted by (C.sub.1 -C.sub.3) alkyl, phenyl or benzyl, or
R.sup.16 and R.sup.17 can, together with the carbon atom that binds them, be (C.sub.3 -C.sub.8) cycloalkyl,
R.sup.18 =(C.sub.1 -C.sub.4) alkyl or (C.sub.1 -C.sub.4) haloalkyl,
R.sup.19 and R.sup.20 =independently H or (C.sub.1 -C.sub.5) alkyl,
R.sup.21 H, (C.sub.1 -C.sub.6) alkyl, (C.sub.3 -C.sub.6) alkenyl or (C.sub.3 -C.sub.6) alkinyl,
R.sup.22 and R.sup.27 =independently of one another, H, (C.sub.1 -C.sub.4) alkyl or halogen, or
R.sup.12 and R.sup.22 can together form a (C.sub.2 -C.sub.3) alkylen,
R.sup.23, R.sup.24 and R.sup.28 =independently of one another, H or (C.sub.1 -C.sub.4) alkyl,
R.sup.25 =(C.sub.1 -C.sub.2) alkyl, (C.sub.1 -C.sub.2) haloalkyl, OCH.sub.3, SCH.sub.3, OCHF.sub.2, halogen, CN or NO.sub.2 and
R.sup.26 =H, (C.sub.1 -C.sub.5) alkyl, (C.sub.1 -C.sub.5) haloalkyl, (C.sub.3 -C.sub.6) cycloalkyl, (C.sub.3 -C.sub.6) halocycloalkyl, (C.sub.1 -C.sub.5) alkoxy, (C.sub.1 -C.sub.5) haloalkoxy and phenyl, that may optionally be substituted up to three times optionally by halogen, NO.sub.2, cyano, (C.sub.1 -C.sub.2) alkyl, (C.sub.1 -C.sub.2) haloalkyl, (C.sub.1 -C.sub.2) alkoxy or (C.sub.1 -C.sub.2) haloalkoxy,
R.sup.29 =H, halogen or (C.sub.1 -C.sub.6) alkyl,
R.sup.30 =H, (C.sub.1 -C.sub.4) alkyl or halogen.
The compounds of formulae I or II are highly active herbicides, which act as protoporphyrinogen oxidase inhibitor and control unwanted grasses and weeds, even when used in small amounts. I and II are, for example, of great interest for cultures with plantations where fast-growing and robust destructive plants impair the harvest. Thanks to the excellent selectivity of type I or II, these compounds can, however, also be used in cultivated plants, for example maize, soya, wheat or barley to combat destructive plants.
2. Related Art
Known processes for the preparation of compound I generally start with an appropriately substituted phenylhydrazine which is converted into the corresponding triazolidinone by reaction with an N-(1-alkoxy)alkylidene alkylcarbamate or with an .alpha.-ketocarboxylic acid derivative and by subsequent Schmidt rearrangement into the corresponding triazolidinones.
EP 0 220 952 for example describes the conversion carried out in xylene of 2-chlorophenyl hydrazine with N-(1-ethoxy)ethylidene ethylcarbamate into triazolinone unsubstituted in 4-position which is then alkylated in an independent reaction step in dimethylformamide into the tri-substituted triazolinone. It is very laborious to prepare bicyclic triazolinones in this manner.
U.S. Pat. No. 4,818,275 and U.S. Pat. No. 4,818,276 also describe processes for substituted triazolinones. Acid condensation of the phenyl hydrazine used with an a-ketocarboxylic acid first yields the hydrazone which undergoes Schmidt rearrangement by reaction with diphenyl phosphorylazide and is hereby converted into triazolinone. The triazolinone formed also has to be alkylated into the final compound in a subsequent reaction step. It is also very laborious to synthesise bicyclic triazolinones in this manner and the azide used causes problems of technical safety when the compounds are synthesised on an industrial scale.
In other known processes for the preparation of individual representatives of compound type II the reaction generally occurs via the corresponding amidrazone which is reacted to bicyclic compounds. ##STR9## DE 28 01 429 describes a process for the preparation of compounds of type II in which it is necessary to react 2-piperidone, that first has to be suitably activated using methods known from the literature (see Houben-Weyl, "Methoden der organischen Chemie", Vol. 11/2, p. 578; and DE-OS 19 12 739 and DE-OS 19 12 737) with the HCl-salt of the correspondingly substituted phenylhydrazine to amidrazone (III) (see DT-OS 22 35 177) and cyclisises the amidrazone formed with chloroformic acid methyl ester or phosgen into THF with addition of base to compounds of type II.
In another process (see PCT/WO 94/22828) N-carboxymethyl-2-iminopiperidine hydrochloride is described as activated intermediate compound. The hydrolysis-sensitive intermediate compound is coupled with the correspondingly substituted phenylhydrazine and then cyclisised by acid catalysis to form triazolinone.
The process according to EP 0 317 947 A2 for the synthesis of triazolinones includes the reaction of N-carboxyalkyl lactams with a phenylhydrazine to amidrazone by boiling under reflux in xylene. The bicyclic triazolinone is formed by reaction with phosgen. A disadvantage of the process is that the condensation step to amidrazone only produces a yield of 21 % in the presence of P.sub.4 O.sub.10 as dessicating agent.
The known processes have the disadvantages that they can, in part, only be realised via long synthesis routes which in part lead via intermediate steps that are laborious to produce and to treat, that they supply moderate yields and in part use costly and not always innocuous starting substances and that various by-products are formed which necessitate laborious purification steps.